Unsaturated imidazolines

ABSTRACT

Compounds having the formula ##STR1## wherein n and m are, individually, 0 or 1, X is an anion, R&#39; is hydrogen, methyl or phenyl and R 2 , R 3  and R 4  are, individually, hydrogen, alkyl, aryl, alkaryl or aralkyl, polymers thereof and methods for their production, are disclosed. The compounds form polymers useful in the treatment of water sludges, the formation of fibers and the treatment of paper.

BACKGROUND OF THE INVENTION

The use of high-efficiency products in the treatment of aqueoussuspensions of particulate, solid, water-insoluble materials has becomeincreasingly prevalent in recent years. Industry, in general, andresearch, in particular, are therefore continually searching for newsystems which can be employed to facilitate the dewatering of aqueoussuspensions of organic, or mixtures of organic and inorganic, materialssuch as distillary wastes, fermentation wastes, wastes from papermanufacturing plants, dye plant wastes and sewage suspensions such asdigested sludges, activated sludges or raw and primary sludges fromsewage treatment plants, etc.

The most recent and most successful materials introduced for thetreatment of such suspensions have been the amidine and imidazolinepolymers, see U.S. Pat. Nos. 3,406,139; 3,450,646; 3,576,740; 3,666,705,hereby incorporated herein by reference. These polymers are veryeffective materials for use in the treatment of industrial wastes. Thepolymers, however, are produced by the treatment of correspondingnitrile polymers and their structures are therefore governed by thestructure of the nitrile polymer from which they are made. Furthermore,conversion of the nitrile polymers to the imidazoline or amidinepolymers does not reach 100 % and a portion of the resultant polymer is,therefore, non-functional in its water treating capacity.

Prior attempts to obviate these difficulties have included rearrangementof the groups present in the nitrile polymer charge and the attemptedproduction of unsaturated imidazolines which may be homopolymerized orcopolymerized into more active imidazoline polymers. Attempts to produceintermediates from which the unsaturated imidazolines may be preparedhave, however, proven unsuccessful. Additionally, attempts to follow theteachings of U.S. Pat. No. 3,210,371 resulted only in the production ofpolymers while the teachings of Oxley et al, Jour. Chem. Soc., 1947,pgs. 497-505 also resulted in the recovery of polymeric products.

SUMMARY

We have now succeeded in the production of a novel class of monomerswhich can be polymerized into polymers useful in the treatment of watersludges, the formation of fibers and the treatment of paper.

DESCRIPTION OF THE INVENTION INCLUDING PREFERRED EMBODIMENTS

The novel compounds of the present invention have the formula ##STR2##where n and m are, individually, 0 or 1, X is an anion, i.e., a negativesalt forming ion or radical, R' is hydrogen, methyl or phenyl and R², R³and R⁴ are, individually, hydrogen, alkyl (C₁ -C₄), aryl (C₆ -C₁₀),alkaryl (C₇ -C₁₁) or aralkyl (C₇ -C₁₁).

The compounds of Formula (I), wherein m is 0, are prepared by heating toa cracking temperature of from about 275° C. to about 500° C., in theabsence of acids or salts, a compound having the formula ##STR3##wherein Y is hydroxyl or RO, R being alkyl (C₁ -C₁₀), aryl (C₆ -C₁₀) oraralkyl (C₇ -C₁₁) and n, R', R², R³ and R⁴ are as set forth above. Thecompounds of Formula (II) are disclosed and claimed in our copendingapplication, Ser. No. 467,332, filed concurrently herewith and entitledCOMPOUNDS, which application is hereby incorporated herein by reference.

These novel compounds (m=0) are preferably prepared at subatmosphericpressure although atmospheric or superatmospheric pressures may be usedunder certain variable conditions, if necessary or desired.

The production of these compounds (m=0) proceeds according to theequation: ##STR4## wherein all variables are as described above.

The charge material of Formula (II) is preferably melted and convertedinto a gas before it is heated to the above described crackingtemperature and passed through an appropriate catalyst. Catalysts whichhave been found to be useful for this purpose can generally be describedas heterogenous vapor phase catalysts. More particularly, they may bedescribed as inorganic oxide gels, alkaline earth metal oxides andmixtures thereof. Examples of materials which have been found to beuseful as catalysts herein include barium oxide, alumina, silica gel,thorium oxide on silica gel, calcium oxide on silica gel, barium oxideon silica gel, barium oxide or alumina and the like. Other relatedcatalysts known to those skilled in the art can also be used.

The product produced according to the above method is usually formed asan admixture with other by-product materials, the desired product beingrecoverable by distillation, extraction, crystallization and the like.

In a preferred embodiment, we have found that the presence of smallamounts of water, i.e. up to about 30%, by weight, based on the totalfeed or charge compound weight, materially enhances the yield of thevinyl (m=0) compound recovered. That is to say, when the charge compoundof Formula (II) contains the above amount of water, preferably fromabout 2.0% to about 30.0%, the yield of Formula (I), m=0, product ismaterially enhanced.

When the unsaturated compounds produced according to Equation A, above,are contacted, usually under ambient conditions, with an acid, e.g.sulfuric, hydrochloric, nitric, acetic, malonic, tartaric, benzoic etc.,the compounds of Formula I, wherein m is 1 are formed. These compoundsalts are preferably produced by merely collecting the effluent from thecracking operation in the appropriate acid, although the vinyl compoundmay be recovered per se and converted to the salt subsequently, ifdesired. It is preferred to convert the vinyl compounds into theircorresponding salts since the salts are more stable than the vinylcompounds per se.

As mentioned above, all the vinyl compounds of Formula (I), above, finduse in the preparation of homopolymers and copolymers thereof. Thecompounds homopolymerize at elevated temperatures spontaneously or theymay be homopolymerized at lower temperatures utilizing free radicalcatalysts, for example, benzoyl peroxide, azobisisobutyronitrile etc.All the vinyl compounds of Formula (I) may be copolymerized with one,two or any desired number of comonomers, the particular number involveddepending on the particular service application to which the copolymersare to be put. When comonomers are used, they may be employed in amountsranging from about 4% to 96%, by weight, based on the total monomercharge, the preferred amount being about 25-75%. Examples of usefulcomonomers which may be copolymerized, preferably under normal vinylpolymerization conditions, include the unsaturated alcohol esters, moreparticularly the allyl, methallyl, crotyl, 1-chloroallyl, 2-chloroallyl,cinnamyl, vinyl, methvinyl, 1-phenylallyl, butenyl, etc., esters ofsaturated and unsaturated aliphatic and aromatic monobasic and polybasicacids such, for instance, as acetic, propionic, butyric, valeric,caproic, crotonic, oxalic, malonic, succinic, glutaric, adipic, pimelic,suberic, azelaic, sebacic, maleic, fumaric, citraconic, mesaconic,itaconic, acetylene dicarboxylic, aconitic, benzoic, phenylacetic,phthalic, terephthalic, benzoylphthalic, etc., acids; the saturatedmonohydric alcohol esters, e.g. the methyl, ethyl, propyl, isopropyl,butyl, sec.-butyl, amyl, etc., esters of ethylenically unsaturatedaliphatic monobasic and polybasic acids, illustrative examples of whichappear above; vinyl cyclic compounds (including monovinyl aromatichydro-carbons), e.g. styrene, o-, m-, and p-chlorostyrenes,-bromostyrenes, -fluorostyrenes, -methylstyrenes, -ethylstyrenes-cyanostyrenes, the various poly-substituted styrenes such, for example,as the various di-, tri-, and tetrachlorostyrenes, -bromostyrenes,fluorostyrenes, methylstyrenes -ethylstyrenes, -cyanostyrenes, etc.,vinyl naphthalene, vinylcyclohexane, vinyl furane, vinyl pyridine, vinyldibenzofuran, divinyl benzene, trivinyl benzene, allyl benzene, diallylbenzene, N-vinyl carbazole, the various allyl cyanostyrenes, the variousalpha-substituted styrenes and α-substituted ringsubstituted styrenes,e.g., α-methyl styrene, α-methyl-paramethyl styrene, etc.; unsaturatedethers, e.g., ethyl vinyl ether, diallyl ether, ethyl methallyl ether,etc.; unsaturated amides, for instance, N-allyl caprolactam, acrylamide,and N-substituted acrylamides, e.g., N-methylol acrylamide,N-allylacrylamide, N-methyl acrylamide, N-phenyl acrylamide, etc.;unsaturated ketones, e.g., methyl vinyl ketone, methyl allyl ketone,etc.; methylene malonic esters, e.g., methylene methyl malonate, etc.;ethylene; unsaturated polyhydric alcohol (e.g., butenediol, etc.) estersof saturated and unsaturated, aliphatic and aromatic, monobasic andpolybasic acids.

Other examples of monomers that can be copolymerized with the monomersof Formula I are the vinyl halides, more particularly vinyl fluoride,vinyl chloride, vinyl bromide and vinyl iodide, and the variousvinylidene compounds, including the vinylidene halides, e.g., vinylidenechloride, vinylidene bromide, vinylidene fluoride and vinylidene iodideother comonomers being added if needed in order to improve thecompatibility and copolymerization characteristics of the mixedmonomers.

Other compounds such as acrylonitrile, and other compounds, e.g., thevarious substituted acrylonitriles (e.g., methacrylonitrile,ethacrylonitrile, phenylacrylonitrile, etc.), the acrylates andmethacrylates including methyl, ethyl, butyl, octyl, etc. acrylate andmethacrylate. Other monomers copolymerizable with the instant novelmonomers are given, for example in U.S. Pat. No. 2,601,572, dated June24, 1952, where examples are given both by classes and species.

Of course, it is also possible to prepare copolymers produced from twoor more of the monomers represented by Formula I, above.

Homopolymers of the Formula I compounds where m=0 may be prepared byheating at a temperature ranging from about 20° C. to about 150° C., inthe absence of a salt or acid, the corresponding vinyl monomer. Suitablecatalysts such as those mentioned above may be used. The copolymers ofthese m=0 compounds may be prepared in the same manner.

Homopolymer salts i.e. where m=1, may be prepared via a plurality ofmechanisms. The particular method employed is not critical except if itis desired to prepare the homopolymer salt from the isolated monomersalt. In such a case, the vinyl monomer where m=0 is merely contactedwith an acid solution or salt solution to form the corresponding vinylsalt which may then be isolated and polymerized. Homopolymer salts mayalso be prepared by heating salts of the compounds represented byFormula II at temperatures ranging from 20°-150° C. alone or in thepresence of a catalyst, e.g. sulfite-bromate-persulfate mixtures, as isknown in the art. The homopolymer salts may also be prepared by heatingthe Formula II compounds in the presence of an acid or salt or bytreating the corresponding homopolymer of the m=0 compound with such anacid or salt. Copolymers of the vinyl salts can be prepared bycopolymerization of the vinyl salt with the above-disclosed comonomersunder the conditions set forth or by contacting the m=0 copolymer with asalt or acid in the same manner as with the homopolymers.

It is therefore apparent that if homopolymers and copolymers of thevinyl monomer where m=0 are to be prepared, it is essential that themonomeric salts or salts per se be avoided in that they tend toimmediately polymerize the vinyl monomers at high temperatures intopolymer salts. However, if isolation of the vinyl monomer where m=0 isnot desired, the salt of the charge materials represented by Formula IIabove may be heated to the above specified cracking temperature in theabsence of a catalyst. In this manner, the hydroxy, alkoxy, aryloxy oralkaryloxy group is cracked, as described above, and the resultant vinylcompound is then immediately polymerized to the homopolymeric salt.

Homopolymeric salts and copolymeric salts, of course, may be convertedinto non-salts by neutralization and dialysis as is known in the art.

The specific homopolymer of 2-vinyl-2-imidazoline produced byhomopolymerizing the monomer where m=0 per se, i.e. that polymer havingthe formula ##STR5## wherein x is the number of recurring units in thepolymer, is distinct from those homopolymers of vinylimidazoline knownin the art and produced by reacting polyacrylonitrile with ethylenediamine since the homopolymer of the instant invention is colorless andis free of ester, carboxyl and amide groups, unreacted nitrile groupsand also unreacted polyamine.

Additionally, the copolymers of the instant invention wherein the vinylimidazoline or vinyl amidine is co-polymerized with acrylamide areequally exceptional in that no such copolymers were even thoughtpossible heretofore since acrylamide-acrylonitrile copolymers do notenable reaction of the nitrile component with a diamine, according toart recognized methods of production, to the exclusion of the acrylamidecomponent.

The novel homopolymers and copolymers of the instant invention find useas water-treatment additives, i.e. flocculation aids and the like andgenerally may be used to facilitate the dewatering of aqueoussuspensions of organic and/or inorganic materials, as mentioned above.They additionally may be used for lowering the cholesterol levels inwarmblooded animals by administering them to said animals inpharmacologically acceptable amounts.

The homopolymers and homopolymer salts of the instant invention have thestructure ##STR6## wherein all substituents are as set forth above.

Similarly, the copolymers have the structure ##STR7## the comonomerbeing any of those mentioned above and the ratio of y:z being 4:96 to96:4, as indicated above. The preferred copolymer exists when thecomonomer is an acrylamide moiety i.e.

The following examples are set forth for purposes of illustrations onlyand are not to be construed as limitations on the present inventionexcept as set forth in the appended claims. All parts and percentagesare by weight unless otherwise specified.

Apparatus and Analytical Methods

The cracking apparatus employed consists of a glass tube fitted withglass joints at top and bottom. The column packing consists of a lowersection (10%) of neutral glass beads, 50% of catalyst and neutral glassbeads (40%) at the top. The upper section of glass beads acts as avaporizer for feed. The column is heated either by a furnace or by alarger diameter glass column which is wrapped with nichrome heatingwire. Temperature measurements are made with a Leeds and Northruppotentiometer equipped with iron constantan thermocouples. Liquid feedis charged dropwise into the column from a heated addition funnel whichhas a pressure equilizing side arm and which is equipped with a glasscapillary tube through which nitrogen can be fed. Product from thecracker is collected in a round-bottomed vessel attached directly to thebottom of the catalyst column by means of the lower joint. This receiveris cooled in a cooling bath while product is collected. Pressure iscontrolled by means of a vacuum pump connected to the receiver and witha manometer equipped with a pressure regulator. Condensates are analyzedby NMR and IR.

EXAMPLE 1

To the above-described apparatus, by way of the heated addition funnel,are added dropwise, 100.0 parts of 2-(2-methoxyethyl)-2-imidazoline. Thecolumn is packed with barium oxide as the catalyst. The temperature ofthe column is 410-425° C. while the pressure (mm Hg) is 0.2. After aperiod of about 4 hours, 50.0 parts of 2-vinyl-2-imidazoline arerecovered. The product is a white, crystalline solid containing a smallamount of liquid.

The 100 MHz 'H NMR spectrum of a CDCl₃ solution (˜5%) of the solid shows8 sharp lines characteristic of the 3 hydrogens in the vinyl group.Their frequency differences (in Hertz) from the internal standardtetramethylsilane are 650, 640, 633, 622, 582, 561, 550. These datayield the following approximate chemical shifts (δ) and couplingconstants (J) for the hydrogens as labelled in the figure: ##STR9## H₁:5.75; H₂ :5.6δ; H₃ :6.4δ; J.sub. 12 :OH₂ ; J₁₃ :18H₂ ; J₂₃ :11H₂. TheNH hydrogen is a broad line at 4.95δ, while the ring --CH₂ --CH₂ --hydrogens appear as a single peak at 3.65δ, indicating the equivalenceof the two CH₂ groups due to rapid exchange of the NH hydrogen. (Atlower concentrations, the exchange is slower, and the removal of the CH₂equivalence is seen as a splitting of the 3.65δ peak into two closelyspaced triplets).

The areas under each of the peaks correspond to the correct numbers ofhydrogens.

EXAMPLES 2-19

Following the procedure of Example 1, various catalysts, pressures andtemperature ranges are employed in the cracking of2-(2-methoxyethyl)-2-imidazoline to 2-vinyl-2-imidazoline. The variablesand results are set forth in Table I, below. In the table, C meanscomparative. In Examples 11-14 and 19, the2-(2-methoxyethyl)-2-imidazoline charge contains 8.8%, 0%, 27.4%, 51.8%and 2.0% water, respectively.

                                      TABLE I                                     __________________________________________________________________________                                        Product                                   Example                                                                            Catalyst    Temperature ° C.                                                                  Pressure mmHg                                                                         Yield                                     __________________________________________________________________________    2    Alumina Extrudate                                                                         290-306    0.2     5.0%                                      3    Alumina Granules                                                                          266-275    0.2     5.0%                                      4    1% Barium Oxide on                                                                        265-274    15.0    25.0%                                          Alumina                                                                  5    Silica Gel  363-384    15.0    83.0%                                     6    24% Thorium Oxide on                                                                      340-380    15.0    40.0%                                          Silica Gel                                                               7    24% Calcium Oxide on                                                                      343-388    15.0    20.0%                                          Silica Gel                                                               8    3.8% Barium Oxide on                                                                      340-374    15.0    63.6%                                          Silica Gel                                                                9 (C)                                                                             Glass Helices                                                                             418-425    0.1     0.0%                                       10 (C)                                                                            Calcium Carbonate                                                                         340-374    15.0    0.0%                                           Chips                                                                    11   Barium Oxide                                                                              330-340    15.0    26.5%                                     12   "           329-324    0.2     13.8%                                     13   Barium Oxide                                                                              326-330    15.0    2.0%                                       14 (C)                                                                            "           334-338    15.0    0.0%                                       15 (C)                                                                            "           269- 278   0.2     0.0%                                      16   "           329-334    0.3     15.0%                                     17   "           358-369    0.2     17.0%                                     18   "           427-431    0.1     43.0%                                     19   "           330-340    15.0    21.0%                                     __________________________________________________________________________

EXAMPLES 20-32

Again following the procedure of Example 1 except that variousalternative charge materials are fed dropwise into the column containingthe cracking catalyst, a series of vinyl imidazolines and amidines areproduced. In each instance, the yield of desired product isquantitative. The charge variables are set forth in Table II, below.

                                      TABLE II                                    __________________________________________________________________________    Charge                                                                        Example                                                                            R    R'  R.sup.2                                                                           R.sup.3                                                                           R.sup.4                                                                           n    Product                                        __________________________________________________________________________    20   CH.sub.3                                                                           H   CH.sub.3                                                                          H   H   O 1-methyl-2-vinyl-2-imidazoline                    21   CH.sub.3                                                                           H   C.sub.7 H.sub.6                                                                   H   H   0 1-benzyl-2-vinyl-2-imidazoline                    22   CH.sub.3                                                                           C.sub.6 H.sub.5                                                                   H   H   CH.sub.3                                                                          0 4(or 5)-methyl-2-(1-phenylvinyl)                  2-imidazoline                                                                 23   CH.sub.3                                                                           H   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          1 1,4,5,6-tetrahydro-1,4,6-tri-                                                 methyl-2-vinylpyrimidine                          24   C.sub.2 H.sub.5                                                                    CH.sub.3                                                                          H   CH.sub.3                                                                          H   1 1,4,5,6-tetrahydro-2-isopro-                                                  penyl-6-methylvinylpyrimidine                     25   CH.sub.3                                                                           CH.sub.3                                                                          C.sub.4 H.sub.9                                                                   H   H   0 1-butyl-2-isopropenyl-2-                                                      imidazoline                                       26   C.sub.4 H.sub.9                                                                    H   H   H   CH.sub.3                                                                          0 4(or 5)-methyl-2-vinyl-2-                                                     imidazoline                                       27   CH.sub.3                                                                           H   C.sub.6 H.sub.5                                                                   H   H   0 1-phenyl-2-vinyl-2-imidazoline                    28   C.sub.6 H.sub.5                                                                    CH.sub.3                                                                          H   H   C.sub.2 H.sub.5                                                                   1 4-ethyl-1,4,5,6-tetrahydro-2-                                                 isopropenylpyrimidine                             29   C.sub.10 H.sub.7                                                                   H   H   H   H   0 2-vinyl-2-imidazoline                             30   C.sub.10 H.sub.21                                                                  H   H   C.sub.7 H.sub.7                                                                   H   0 4(or 5)-tolyl-2-vinyl-2-                                                      imidazoline                                       31   C.sub.7 H.sub.7                                                                    H   C.sub.10 H.sub.7                                                                  H   H   0 1-naphthyl-2-vinyl-2-                                                         imidazoline                                       32   CH.sub.3                                                                           H   H   C.sub.11 H.sub.9                                                                  H   0 4(or 5)-(naphthylmethyl)-2-                                                   vinyl-2-imidazoline                               __________________________________________________________________________

EXAMPLE 33

The procedure of Example 1 is again followed except that the2-vinyl-2-imidazoline product is allowed to collect in a round-bottomvessel containing sulfuric acid. A stable, white, crystalline solid isthen recovered and shown to be 2-vinyl-2-imidazoline sulfate. A solutionof this 2-vinyl-2-imidazoline sulfate salt (14.0 weight percent) ischarged to a suitable polymerization vessel equipped with a stirrer andmeans for deaeration. After adjusting the pH to 3.0 with 50% aqueoussodium hydroxide solution and then deaerating with a stream of nitrogenfor 2 hours, polymerization is initiated by adding 16.7 ppm (based onimidazoline salt) of sodium sulfite followed by 263 ppm each (based onimidazoline salt) of sodium bromate and ammonium persulfate. Afterpolymerizing 2 days at room temperature, the syrupy polymer solution isconcentrated by evaporation under vacuum to a more viscous syrup fromwhich the polymer is precipitated by pouring into an excess of ethanolin a Waring blendor. After filtration followed by drying in vacuo overcalcium chloride, the polymer consists of light yellow-colored granules.The polymer is redissolved in water, reprecipitated into ethanol,filtered and dried in vacuo. This treatment produces a white polymerwith an intrinsic viscosity of 1.30 dl/gm in 1N NaCl solution. NMR andIR analysis of the polymer show that it is the sulfate salt ofpoly(2-vinyl-2-imidazoline) uncontaminated by nitrile, diamine, ester oramide groups. It should be noted that the structure of our polymer,i.e., ##STR10## is different from that of the art, see especially U.S.Pat. No. 3,450,646, which claims the following structure ##STR11## BothNMR and IR spectra show that the above structure is absent from theinstant homopolymer.

The polymer effectively clarifies raw water.

EXAMPLE 33A

Into a suitable distillation vessel equipped with a condenser and dryice-cooled receiver are weighed 3.0 parts of2-(2-methoxyethyl)-2-imidazoline hydrochloride (m.p. 102.5°-104° C.). Apre-heated oil bath at a temperature of 183° C. is used to heat thedistillation vessel for 35 minutes, during which time the contentsbubble and become viscous and condensate collects in the receiver. Thiscondensate is identified as a 75/25 methanol/water solution by IR. Theyellowish-colored resin remaining in the vessel is completelywater-soluble and is identified as poly(2-vinyl-2-imidazoline)hydrochloride: ##STR12## contaminated with a small amount of startingmaterial. This polymer is an effective clarification aid for raw water.

The polymers of Examples 33 and 33A are 100% poly(2-vinyl-2-imidazoline) salts, uncontaminated by nitrile, amide or estergroups or by ethylenediamine salts, or yet further by imino or ketonicgroups along the carbon backbone of the polymer. In this regard, theyare different from the poly 2-vinyl-2-imidazoline salts disclosed inU.S. Pat. No. 3,406,139, where the imidazoline or pyrimidine saltpolymers are prepared from preformed polyacrylonitrile. It has beenrecently demonstrated that polyacrylonitrile manufactured by freeradical polymerization techniques contains imino (=NH) and/or ketonicgroups along the polymer backbone, see On The Chromophore ofPolyacrylonitrile III, The Mechanism of Ketone Formation inPolyacrylonitrile, J. Brandrup J. R. Kirby and L. Peebles, Jr.;Macromolecules 1, 59-63, (1968); Side Reaction in Acrylonitrile RadicalPolymerization, L. Patron and M. Bastianelli, Paper presented at theA.C.S. Special Symposium on Acrylonitrile in Macromolecules, 166thA.C.S. National Meeting, Chicago, Illinois, August 27-29, 1973.

These defects along the backbone of the polyacrylonitrile carbon-carbonbackbone are postulated to arise from occasional so-called abnormalreactions: ##STR13## Since polyacrylonitrile itself is not 100% pure(some of the nitrile groups have taken part in "abnormal" reactionsduring polymer synthesis) and since very few chemical transformations goto 100% conversion, the polyvinylimidazoline salts of the prior artcannot be 100% pure poly 2-vinyl-2-imidazoline salts as are the polymersof the instant examples.

EXAMPLES 34-46

The monomers of Examples 20-32 are individually contacted with aqueousacid solution in order to convert them to their corresponding salts asset forth in Example 33 except that the salts are isolated and recoveredrather than homopolymerized. The compounds produced are:

(34) 1-methyl-2-vinyl-2-imidazoline nitrate;

(35) 1-benzyl-2-vinyl-2-imidazoline acetate;

(36) 4 (or 5)-methyl-2-(1-phenylvinyl)-2-imidazoline sulfate;

(37) 1,4,5,6-tetrahydro-1,4,6-trimethyl-2-vinylpyrimidine nitrate;

(38) 1,4,5,6-tetrahydro-2-isopropenyl-6-methylvinylpyrimidine sulfate;

(39) 1-butyl-2-isopropenyl-2-imidazoline citrate;

(40) 4 (or 5)-methyl-2-vinyl-2-imidazoline tartrate;

(41) 1-phenyl-2-vinyl-2-imidazoline acetate;

(42) 4-ethyl-1,4,5,6-tetrahydro-2-isopropenylpyrimidine malonate;

(43) 2-vinyl-2-imidazoline benzoate (10% solution of benzoic acid indimethyl formamide used);

(44) 4 (or 5)-tolyl-2-vinyl-2-imidazoline nitrate;

(45) 1-naphthyl-2-vinyl-2-imidazoline citrate;

(46) (or 5)-(naphthylmethyl)-2-vinyl-2-imidazoline tartrate.

EXAMPLE 47

A solution of 17.0 parts 2-vinyl-2-imidazoline, 43.0 parts of styreneand 140.0 parts of toluene is prepared in a suitable polymerizationvessel equipped with means for stirring and deaeration and temperaturecontrols. After deaeration for 1 hour with a stream of nitrogen, thetemperature is raised to 60° C. and polymerization is initiated by theaddition of 100 ppm (based on total weight of imidazoline) ofazobisisobutyronitrile as a 1.0% solution in methanol. After allowingthe polymerization to proceed overnight at a temperature of 60°-70° C.,the polymer is precipitated from the resulting viscous solution bypouring it into an excess of methanol with vigorous stirring. Theresultant yellowish colored polymer is redissolved in toluene and thenreprecipitated once more by pouring into methanol. IR and NMR analysisof dried polymer show about 75 mole percent styrene and 25 mole percent2-vinyl-2-imidazoline incorporated into the copolymer. A sample of thepolymer is an effective sizing agent for 50/50 Albacel-Astracel pulp(bleached hardwood-softwood Kraft pulp).

EXAMPLE 48

A solution of 14.7 parts of 2-methoxyethylimidazoline and 0.15 parts ofdistilled water are fed to the cracking apparatus described above at381°-386° C. and at 16 mm Hg pressure. Effluent from the crackingoperation is collected in a flask which contains 109.2 parts of 10.32%sulfuric acid which has been cooled in ice water. The resultant solutionof 2-vinyl-2-imidazoline sulfate is extracted once (40 minutes at roomtemperature) with 2.0 parts of activated carbon which had previouslybeen treated with dilute sulfuric acid followed by 0.1% copper sulfatesolution (7:1 weight ratio of copper sulfate solution to activatedcarbon) so as to render the activated carbon inactive as a cause ofpolymerization. The resultant solution after filtration has a ph of 0.8,a slight greenish-yellow color and analyzes 4.23% 2-vinyl-2-imidazoline(as the free base) by NMR.

To 80.2 parts of the 2-vinylimidazoline sulfate solution are added 46.9parts of dry acrylamide crystal and 227.9 parts of deionized water.After solution is complete, the pH is 1.50. 5.03 Parts of 50% sodiumhydroxide solution are added so as to raise the pH to 3.00. Theresultant solution is deaerated with a stream of nitrogen in a suitablepolymerization vessel and polymerization is initiated by aqueoussolutions of sodium sulfite, ammonium persulfate and sodium bromate (8ppm of sodium sulfite and 155 ppm each of persulfate and bromate, basedon imidazoline salt charged). After 15 hours, a tough rubbery gel isobtained. A portion of this gel is extracted with methanol, dried invacuo and milled. A solution (0.10% in 1N NaCl) of the resultant whitepowder has a viscosity of 2.63 cps. when measured with a Brookfield LVTviscometer with UL adapter at 60 rpm and 25° C. By IR analysis, thecopolymer contains 5-10% of 2-vinylimidazoline sulfate while NMRanalysis substantiates this result. The copolymer effectively clarifiesbrackish water.

EXAMPLE 49

The copolymer of Example 48 is added (0.11% on dry sludge solids) to NewRochelle mixed primary digester sludge and proves to be an effectivedewatering aid. Homopolymeric acrylamide is ineffective when used aloneon this sludge.

EXAMPLE 50

Following the procedure of Example 1, 16.46 parts of feed consisting of6.5% water and 93.5% of 2-(2-methoxyethyl)-2-imidazoline, is crackedover a regenerated silica gel at 364°-384° C. and a pressure of 13-15 mmHg. The brown, semi-crystalline condensate which results is analyzed byNMR which indicates an 85% conversion to 2-vinylimidazoline at aselectivity of 98%.

The condensate is dissolved in 250 parts of anhydrous diethyl ether andthe solution is poured into a solution of 30.0 parts of 15.75% (W/W)anhydrous hydrochloric acid in anhydrous diethyl ether and 70 parts ofanhydrous diethyl ether. A crystalline precipitate forms immediately.The precipitate, 2-vinyl-2-imidazoline hydrochloride is filtered througha fritted glass funnel and the crystals are washed several times withfresh diethyl ether.

A solution of 3.55 parts of dry acrylamide crystal in 30 parts ofdeionized water is prepared in a suitable reaction vessel equipped withstirrer, thermometer, addition funnel, nitrogen inlet and outlet andcooling bath. A solution of 6.6 parts of the 2-vinyl-2-imidazolinehydrochloride in 20 parts of deionized water is placed in the additionfunnel. The two solutions are deaerated with nitrogen and thetemperature is adjusted to 31° C. Polymerization of the acrylamide inthe vessel is initiated by the addition of 6.2 ppm of sodium sulfite and79 ppm each of ammonium persulfate and sodium bromate (based on chargedmonomer). Cooling is initiated and the 2-vinyl-2-imidazolinehydrochloride solution is added incrementally over 50 minutes while thevessel is maintained at 30.5°-32° C. After all the monomer salt isadded, an additional charge of catalyst equal to the first is chargedand the copolymerization is allowed to proceed overnight. Afterprecipitation of the resultant copolymer in methanol-ether, washing,filtering and drying, IR analysis shows a copolymer of 50%acrylamide-50% 2-vinyl-2-imidazoline hydrochloride.

EXAMPLE 51

Use of the copolymer of Example 50 as a dewatering aid on New Rochellesludge shows excellent results.

EXAMPLE 52

A solution of 10.0 parts acrylamide, 0.12 part of a commerciallyavailable anionic emulsifier and 41.7 parts of deionized water isprepared in a suitable polymerization vessel equipped with means forstirring, monomer addition, deaeration and temperature control. Afterthe acrylamide and anionic emulsifier have dissolved, a solution of 2.25parts of 2-vinyl-2-imidazoline sulfate at pH 3.5 is added. Afterdeaeration for 30 minutes at room temperature, 1.83 parts of styrene areadded, then the solution is heated to 75° C., when 0.19% (based on totalweight of monomers) as a 2.0% aqueous deaerated solution is added. Thetemperature is controlled at 74°-85° C. for 4 1/2 hours and then allowedto cool down to room temperature overnight. The reaction mixture is aturbid viscous solution. A sample of the polymer solution is tested as adry strength agent for tissue paper and is found to be effective.Another sample of the terpolymer is an effective drainage aid forunbleached Kraft linerboard stock with 3 % black liquor, 1% alum and atpH 5.5

EXAMPLE 53

A solution of 1.16 parts of 1,2-dimethyl-2-imidazoline in 7.0 parts ofbenzene is prepared in a round-bottomed distillation flask and then 0.47part of paraformaldehyde and 0.05 part of phenothiazine are added. Afterconnecting the flask to an 8 inch, glass-helices-packed column equippedwith a reflux head, the mixture is heated to reflux for half an hourduring which time a solution is obtained. After standing and coolingovernight, the solution is reheated to reflux for half an hour, by whichtime the theoretical amount of water of reaction has been recovered. IRanalysis of the reaction mixture indicates almost 100% conversion ofstarting material to mainly 2-(2-hydroxyethyl)-1-methyl-2-imidazoline.

The benzene is stripped from the reaction mixture and then the highboiling residue is heated to 170°-194° C. overnight during which timewater distills out. No 2-vinyl-1-methyl-2-imidazoline is recovered. Ahard brittle resin remains in the distillation flask. This resin isdissolved in isopropyl alcohol and precipitated in diethylether twiceand then dried in vacuo overnight. IR analysis of the polymer shows itto be poly(2-vinyl-1-methyl-2-imidazoline).

The polymer is shown to be an excellent dewatering aid when used totreat organic waste contaminated water.

EXAMPLE 54

Following the procedure similar to that of Example 48, a solution of 225parts of 2-vinyl-2-imidazoline sulfate, 56 parts acrylamide and 168parts of deionized water, after adjusting the pH to 3.0, is placed in asuitable polymerization vessel and deaerated with a stream of nitrogenfor 2 hours. Polymerization is initiated at room temperature by adding14.0 ppm of sodium sulfite and 280 ppm each of sodium bromate andammonium persulfate (based on total weight of monomers charged). Afterpolymerization is complete (overnight), a tough rubbery gel, from whichthe polymer is isolated by the same procedure as in Example 48, isobtained. The viscosity of a 0.10% solution of the dried polymer in 1NNaCl at 25° C. using a Brookfield LVT viscometer with UL adapter at 60rpm is 2.56 cps. Both NMR and IR analyses confirm that the polymercontains 5-10 mole percent poly 2vinyl-2-imidazoline sulfate (NMR givesabout 7.5 mole percent and IR 5-10 mole percent).

A sample of this polymer is tested as a drainage and retention aid forEucalyptus pulp and gives the results in Table III, below. This pulp hasa Canadian Standard Freeness (CSF) of 310 ml and the conditions are: 10%clay, 1% rosin size, 2% alum and pH 4.8.

                  TABLE III                                                       ______________________________________                                        The Effectiveness of 92.5/7.5 Acrylamide/2-Vinyl-2-Imidazoline                Sulfate Copolymer as a Drainage and Retention Aid                             Polymer Added-                                                                % on Dry Fiber                                                                           Drainage-Time Secs.                                                                           Clay Retained-%.sup.1                              ______________________________________                                        0          44.4            7.64                                               0.02       32.6            8.14                                               0.04       29.0            8.14                                               0.06       28.2            8.20                                               0.08       28.0            8.20                                               0.10       30.3            8.19                                               ______________________________________                                         .sup.1 Determined by ashing samples of dried treated pulp.               

Another sample of the same polymer is tested as a drainage aid for "oldnews", recovered newspaper pulp, at pH 7 and gives the results listed inTable IV, below.

                  TABLE IV                                                        ______________________________________                                        The Effectiveness of a 92.5/7.5 Acrylamide/2-Vinyl-2-Imidazolin               Sulfate Copolymer as a Drainage Aid                                           Conditions:                                                                           "Old News" pH 7.0                                                             A blank took 51 secs. to drain.                                       Polymer Added- Improvement in                                                 % on Dry Fiber Drainage-Seconds                                               ______________________________________                                        0.05           21                                                             0.10           28                                                             0.15           34                                                             0.20           37                                                             0.25           40                                                             0.30           41                                                             ______________________________________                                    

A third sample of the same polymer is tested as a drainage aid for oldnews with 2% alum, 1% rosin size and pH 4.5 and gives the results listedin Table V, below.

                  TABLE V                                                         ______________________________________                                        The Effectiveness of a 92.5/7.5 Acrylamide/2-Vinyl-2-Imidazoline              Sulfate Copolymer as a Drainage Aid                                           Conditions:                                                                           2.0% alum, 1.0% rosin size, pH 4.5                                            A blank took 37 secs. to drain                                        Polymer Added- Improvement in                                                 % on Dry Fiber Drainage-Seconds                                               ______________________________________                                        0.05           20                                                             0.10           23                                                             0.15           24                                                             0.20           24                                                             0.25           12                                                             ______________________________________                                    

Polyacrylamide containing no cationic comonomer is ineffective as adrainage aid; the drainage time actually increases.

EXAMPLE 55

To a solution of 26.0 parts of a commercially available mineral oilsolvent and 2.6 parts of a commercially available fatty acid sorbitansurfactant is added a solution fo 24.4 parts of acrylamide in 24.4 partsof deionized water and 18.1 parts of 2-vinyl-2-imidazoline sulfatesolution prepared and purified as in Example 48. Before adding theaqueous solution to the hydrocarbon solution, the pH is adjusted to 3.5and 30 ppm of ethylenediamine tetraacetic acid (based on total monomer)are added. The two solutions are placed in a suitable polymerizationvessel and stirred vigorously so as to obtain a smooth emulsion. Afterreducing the stirring speed, 100 ppm of sodium bromate (based on totalmonomer) are added as a 0.87% aqueous solution and then the emulsion isdeaerated with a stream of nitrogen for 1.2 hours at room temperature.During the next 6.7 hours, 120 ppm sodium bisulfite, as an 0.205%aqueous solution, are fed in and the temperature is allowed to increaseto 40° C. at which point cooling is started and maintained for about 40minutes. Thereafter, for the remainder of the 6.7 hours, thepolymerization proceeds without cooling. A smooth, coagulum-free,polymer emulsion is obtained and the conversion of monomer to polymer is97.7%. The viscosity of a 0.10% (real polymer basis) solution in 1N NaClat 25° C. using a Brookfield viscometer with UL adapter at 60 rpm is 2.6cps. The molar composition of this polymer is 95/5acrylamide/2-vinyl-2-imidazoline sulfate.

EXAMPLE 56

Following the procedure of Example 55, a 90/10acrylamide/2-vinyl-2-imidazoline sulfate copolymer emulsion is prepared,but in this case a small amount of coagulum is formed. The viscosity ofa 0.10% solution (dry polymer salt basis) in 1N NaCl at 25° C. usingBrookfield LVT viscometer with UL adapter at 60 rpm is 2.2 cps and theconversion of monomer to polymer is 97.8%.

Samples of the polymers from Examples 54, 55 and 56 are tested as sewagesludge dewatering agents on Greenwich, Connecticut mixed primary wasteactivated sludge containing 2.5% solids. The results of the tests arepresented in Table VI, below. Polyacrylamide containing no cationiccomonomer residues is ineffective in dewatering this sludge. The test isa standard Buchner funnel filtration test utilizing 150 ml of sludgemixed with 30 ml of a solution of the polymer to be tested for eachdosage level.

                                      TABLE VI                                    __________________________________________________________________________    Evaluation of Various Polymers as                                             Sewage Sludge Dewatering Agents                                               Greenwich, Conn. mixed primary waste activated sludge (2.5%                   solids)                                                                                   MI Filtrate Collected in 1 Minute                                 Dosage, lb. Polymer                                                                       Polymer From                                                                          Polymer From                                                                          Polymer From                                      Ton Sludge Solids                                                                         Example 54                                                                            Example 55                                                                            Example 56                                        __________________________________________________________________________    0           14      14      14                                                3.21        38      22      20                                                6.42        60      29      --                                                9.63        65      --      24                                                12.8        115     43      --                                                19.3        130     --      28                                                25.7        106     74      --                                                48.2        --      132     78                                                __________________________________________________________________________

EXAMPLE 57

The 1-methyl-2-vinyl-2-imidazoline of Example 20 (100 parts) is fed intoa suitable reaction vessel equipped with a stirrer and deaeration means.The vessel is deaerated as in Example 33 and 92.0 ppm ofazobisisobutyronitrile and 150 parts of toluene are added. Thepolymerization reaction is allowed to proceed for 36 hours at 57° C.after which time the polymer is recovered by precipitation frommethanol. Analysis shows a homopolymer of 1-methyl-2-vinyl-2-imidazolinefree of nitrile, amide or ester groups. No imino or ketonic groups aredetected in the polymer backbone. The homopolymer effectively aids indewatering high solids sludge.

EXAMPLES 58-67

Following the procedure of Example 57, the vinyl imidazolines orunsaturated pyrimidines of Examples 21-32 are homopolymerized intopolymers. The homopolymers are all free of nitrile, amide or estergroups. Each product exhibits the ability to assist in dewateringorganic waste sludge.

EXAMPLES 68-77

The monomers of Examples 21-32 are copolymerized with styrene accordingto the procedure of Example 47. Similar results are attained. Theresultant copolymers exhibit the usefulness shown for the polymer ofExample 47.

EXAMPLES 78-90

Following the procedure of Example 52, the monomers of Examples 34-46are copolymerized with acrylamide. The resultant copolymers are shown tobe effective dry strength agents and drainage aids.

EXAMPLES 91-103

Following the process set forth in Example 33A, the monomers of Examples34-46 are homopolymerized into polymers uncontaminated by nitrile, amideor ester groups or ethylenediamine salts or imino and ketonic groups.They are effective water clarifiers.

We claim:
 1. A compound having the formula ##STR14## wherein m is 0 or1, n is 0, X is an anion, R' is hydrogen or methyl and R³ and R⁴ are,individually, hydrogen, alkyl (C₁ -C₄), aryl (C₆ -C₁₀), aralkyl (C₇-C₁₁) or alkaryl (C₇ -C₁₁).
 2. A compound according to claim 1 whereinR' is hydrogen.
 3. A compound according to claim 1 wherein m is
 0. 4. Acompound according to claim 1 wherein R³ and R⁴ are each hydrogen.
 5. Acompound according to claim 1 wherein m is 0, and R', R³ and R⁴ are eachhydrogen.